Vat dye compositions containing benzotriazoles



2,940,815 Patented June 14, 1960 VAT DYE COMPOSITIONS CONTAININGBENZOTRIAZOLES John Taras, Alpha, N.J., assignor to General Aniline &Film Corporation, New York, N.Y., a corporation of Delaware No Drawing.Filed Dec. 4, 1953, Ser. No. 396,350 6 Claims. (Cl. 8-35) This inventionrelates to vat dye compositions and particularly to vat dyestuficompositions containing benzotriazoles for the printing of textilefibers.

The printing of textile materials with ester salts of leuco vatdyestufis is well known to the art. The process involves dissolving theester salt of the leuco vat dyestufi in water and adding a thickeningagent to form the printing paste which is applied to the textilematerial in several known ways, after which the insoluble parent vatdyestufi is fixed on the fibers by the hydrolysis and oxidation whichtakes place in the ageing process which is generally one of two kinds.In the acid ageing process for the development of the print, acid steamis applied along with treatment of the impregnated fabric with an acidsolution of an oxidizing agent. Where an acid-liberating agent and anoxidizing agent have been incorporated in the printing paste,development of the print takes place with the application of ordinarysteam. The printed material is then rinsed, soaped and finished.

The solubility in water of the ester salts of the leuco vat dyestuffs isdue to the presence in the molecule of one or more polybasic and estergroups. This solubility varies, widely and is dependent chiefly on thecharacter of the parent vat dyestuff. In the case of the sodium salts ofthe sulfuric acid esters of the leuco vat dyestuffs, some of these areeasily soluble in water, whereas others, being considerably lesssoluble, are readily salted out by the presence in the printing paste ofelectrolytes usually employed in the printing, most commonly ammoniumthiocyanate for the acid-liberating function, and sodium chlorate forthe oxidation step. The selection of vat dyestufis for use in theprinting of textiles is accordingly limited to those, the leuco estersalts of which possess the required solubility in water.

In the interest of providing stable printing pastes containing a solublesalt of the sulfuric acid ester of leuco vat dyestuffs and of employingtherein leuco ester salts of low solubility, thus to provide a Widerrange of selection in the vat dyestuffs, more work has been done by wayof adding to the printing compositions various quantities of organicsolvents such as alcohols, ethylene glycol, etc., and of other printingassistants of a variety of chemical species. Despite the many excellentprinting assistants which have been added to printing pastes, there arecertain vat dyestufls, for example, 2,.1naphthio-indigo, which yieldsulfuric acid ester salts which are so diflicultly soluble in Waterwhich renders printing impossible unless there is formulated into theprint paste certain so-called solubilizing agents.

I have found that improved dyestutf compositions containing salts ofpolybasic acid esters, especially sulfuric acid esters of leuco vatdyestuffs (hereinafter referred to for sake of simplicity as ester saltsof leuco vat dyestulis) are readily obtained by incorporating with theester salt of the leuco vat dyestuff a benzotriazole which ischaracterized by the following general formulae:

N N a f N-R and N R" N N I H R 0 wherein R represents either hydrogen,lower alkyl, e.g.,

.methyl, ethyl; hydroxy, hydroxyphenyl, or acetyh-R .represents eitherhydrogen, lower alkyl as in R or .car-

boxymethy-l, and R" represents aryl of the benzene series, e.g. phenyl,tolyl, hydroxyphenyl, carboxyphenyl, etc.

As examples of such benzotriazoles the following are illustrative:

The incorporation of the foregoing 'benzotriazoles into compositions ofester salts of leuco vat dyestuffs not only improves the solubility ofthe less soluble ester salts of the leuco vat dyestuifs, but also'yields superior print paste stability, superior tinctorial quality ofthe textile prints, both in respect to tinctorial strength andbrilliancy, and superior print paste solubility.

The benzotriazole compounds may be incorporated directly into theprinting pastes, or they may be first mixed with the ester salt of theleuco vat dyestufi. They may be used singly or in admixture with oneanother. The amount of the benzotriazoles or mixtures thereof which maybe incorporated into the dyestutf composition may be very considerable.For example, the amount utilized in one case may depend upon thesolubility of the ester salt of the vat dyestuff as well as the activityof the particular benzotriazole or benzotriazole mixture employed. Forpractical purposes regardless of the solubility of the ester salt of thevat dyestutf, we have found that superior print paste solubility,superior tinctorial properties and superior print paste stability areobtained when from about one-quarter to four parts by weight of thebenzotriazole compound or mixtures thereof are used for each part of theparent vat dyestufl of the ester salt. In addition, in many cases anexcess of the benzotriazole or mixtures thereof may be used, the excessmerely acting as a diluent. The unusual aspect of the benzotriazoles andmixtures thereof is that they do not interfere with the other agentsnormally employed in the preparation cf'printingpastes containing saltsofsulfurieaidesters leuco vat salts of vat dyes 'p'ared'by careful 7basic acid esters may 'indigoid or thioindigoid dyestuffs,

' 441,101, 516,845, 486,174, 491,876, and the like.

pastes or powders with these vat benzotriazoles or mixtures thereof maybe used to replace part of the water or the solid diluent in thestandardization of the dyestufi composition. Additional substanceshaving diluent, anti-foaming, wetting, catalytic or other desiredaction, may be included in the dyestufi compositions prepared inaccordance with the present invention,

The various substances that may be so employed are well known to the artand need not be exemplified herein.

However, for purposes of specific illustration such substances as sodiumsulfate or sodium carbonate will serve as diluents or alkaline agents,organic fillers such as dextrose, dextrinesand the like, and catalyticsubstances such as ammonium vanadate and the like. a

The ester salts of leuco vat dyestuffs useful in the prep 'aration oftheprinting pastecompositions of the present invention include all of thosethat are prepared from vari- Thus, in' preparing printing 7 dyestuifester salts, the,

dus clasess of vat dyestuffs such as, for example, vat dyestuifscontaining the anthraquinone-acridine, dibenzanthrone,isodibenzanthrone, anthanthrone, dianthraquinone-azine,anthraquinone-diphenylthiazole, nucleus and the like, which may be foundin various literature including the Colour Index No. 109413 and 1 l77ff,pages Inclusive of such dyes "are also leuco ester acidification of analkaline 'vat. "A particularly valuable class of these ester compoundsof the metal, such as sodium and potassium and aniine salts, such astrimethyl amine'and triethanol amine salts of polybasic acid esters ofleuco vat dyestuffs.

be prepared either from sulfuric or phosphoric acid. 7

By the term leuco vat dyestuif as employed herein is meant the reducedor vattedform o'f anthraquinone,

such as those described in U.S.P. 1,639,206; 1,668,392, 1,747,107,1,646,018, 1,448,251, 1,448,231, 1,880,996, 1,826,720; British Patents473,471 and 438,841, German Patents While the benzotriazoles of thepresent invention maybe used with all of the classes of salts of estersand leuco vat dyestufis they are especially adaptable for the lesssoluble leuco vat dyestuffs. r I As specific examples of the salts ofthe polybasic acid esters of the lueco form of vat dyes which may beempldyed in the preparation of printing paste compositions, thefollowing are illustrative:

'(1) The disodium salt of the disulfuric acid ester-of the leuco form ofthe anthraquinone-acridine dye of the following formula:

and leuco compounds of vat dyes pre- .The polyx;

of the leuco form of 4, the dinaphthioindigo of the follow- 1 ingformula: V r a I "(3) Disodium salt of sulfuric acid ester of the leucoform of 2,1,5,4-anthraquinone-di-phenylthiazole' of the followingformula:

(4) Disodium salt ofthe sulfuric-acid ester of the leuco form of thedibromo-anthanthrone of the following r formula:

(5') Disodium salt of the sulfuric acidof thezleuco compound ofchlorinated iso-dibenzanthrone of the following formula: a

(6) Tetra-potassium salt of the sulfuric acid ester of3,3'-dichloro-di-anthrahydroquinone azine of the following formula:

V O V V V (8) Dipotassium salt of the acid sulfuric acid ester of theleuco compound of dimethyl-dibenzanthrone of the following formula:

(9) Dipotassium salt of the sulfuric acid ester of the leucoform ofdinaphthioindigo of illustration (2).

The following examples will show the manner in which the presentinvention may be practiced. All the parts given therein are by weightunless otherwise specified. It is to be noted, however, that theinvention is not to be limited to these examples sincev many changes maybe made in the materials treated and their proportions, manipulativesteps, and other conditions without departing from the scope and spiritof the invention claimed.

Example I The solution is then mixed with 60 parts of starch-tragacanththickening and 4 parts of a sodium chlorate solution 2 parts 1% ammoniumvanadate solution 2 parts 28% ammonia 2 parts 50% gluconic acid solutionB. A print paste is prepared as in A with the exception that thebenzotriazole is omitted.

Cotton cloth is printed with a portion of each of the printing pastes Aand B. After drying, the printed cloth is subjected to a steam ageingprocess by exposing it for about 10 minutes to the action of steam. Thedevelopment is complete after the cotton cloth is subjected to rinsing,soaping and finishing in the usual manner.

The printing paste prepared from the dyestufi composition A containingbenzotriazole yields an olive green shade which is stronger, brighterand more level than that produced with the printing paste made from thedyestutr' composition B not compounded with the benzotriazole.

Example II A. A powdered dyestufl composition is prepared by grindingtogether in the dry state, screening and milling.

100 parts of a dry dyestuif composition containing 49.2 parts of thesame parent vat dye used in Example I 48 parts of l-methyl benzotriazole13 parts Cerelose (d-glucose powder) The final concentration of the vatdyestuff in the dry composition is 26.6%.

B. A powdered dyestufi composition is made up as in A with the exceptionthat the 'l-methyl benzotriazole is omitted and parts d-glucose added,so that a total of 53 parts of the diluent, d-glucose is present Theconcentration of the vat dyestuff in the dry composition is the same asin A (26.6%).

A printing paste is prepared from each of these dyestulf compositions, Aand B, in the following manner:

4 parts each of the dyestufl compositions A and B is separately mixedwith 4 parts urea and finally dissolving by adding 18 parts Warm Waterand holding in a boiling bath for two minutes These solutions are theneach mixed with:

69 parts starch tragacanth thickening and 4 parts of a 35% sodiumchlorate solution 2 parts 1% ammonium vanadate solution 2 parts 28%ammonia 2 parts gluconic acid solution Cotton cloth is printed with aportion of each of the printing pastes as they are prepared. Theprinting is performed as in Example I.

The printing paste prepared from the dyestufi composition A containingl-methyl benzotriazole yields an olive green shade which is stronger,brighter and more level than that produced with the printing paste madefrom the dyestufi composition B not compounded with l-methylbenzotriazole.

Example 111 A. A print paste is prepared from the following dyestuifcomposition:

4 parts of a dry dyestufif composition containing 1.06 parts of the samevat dyestufi used in Example I 2 parts l-ethyl benzotriazole 4 parts[3,5'-dihydroxydiethylsulfide 4 parts urea and finally dissolving byadding 15.0 parts warm water and holding in a water bath for two minutes'2 parts 50% gluconicacidjsolution I The solution is then mixed with:

"60 parts starch tragacanth thickening and 4 parts 25% sodium chloratesolution 7 7 V w p i 2 parts 1% ammonium vanadate solution 1 part 28%ammonia and N 4 parts ammonium sulfocyanide B. A print paste ispreparedv as withithe eirception that the l-ethyl benzotriazole, isomitted andwater is sub- 1 stituted for it. a V A Cotton prints arermadefromjeach of these printing compositions. V I a The cottonprints'obtained from the composition A formulated with l-ethylbenzotriazole are stronger and brighter than thoseobtained from. B. 7 a

Example I V; v

A. A print paste is prepared as follows:

4 parts of a paste composition containing the 'dipotas sium salt of theacid'sulfuric acid ester of the leuco compound ofdimethoxy-dibenzanthrone of illustration 7 (equivalent to'0.54 part oftheparent vat dye) /2 part l-hydroxy benzotriazole 4' parts urea andfinally dissolving by adding 16,5 parts warm water and holding inaboiling water bathfor2minutes- The solution is then mined with I .4. I

' Example V1 A. A print paste is prepared fronithe following dyestuficomposition:

4 parts of a dry dyestufi composition containing the disodium saltof theacid sulfuric acid ester of the leuco compound of chlorinatedisodibenzanthrone (mixture of diand tri-chlorinated iso-dibenzanthrone)of illustration (equivalent to 1.05 parts of the parent vat dye) V 2parts l-acetyl benzotriazole 4 parts ,B,B'-dihydroxy-diethyl sulfide 4parts urea and finally dissolving by adding 16 parts warm water andholding in a boiling water bath for 2 minutes The'solution is then mixedwith 60 parts starch tragacanth'thickening and 4 parts of a 35% sodiumchlorate solution 2 parts 1% ammonium vanadate solution 2 parts 28%ammonia 2 parts 50% gluconic acid solution tame A. A print paste isprepared from the following dyestuff composition:

4 parts of the same drydyestuff composition used in Example V 1 partZ-phenyl-benzotriazole-1-oxide 4 parts 18, 3'-dihydroxy-diethyl sulfide.4 parts urea and finally dissolving by adding 0 16 parts warm water andholding in a water bath for 2 minutes The solution is then mixed with 60parts starch tragacanth thickeningand 4 parts 25% sodium chlorate.solution 2 parts 1% ammonium vanadate solution 1 part 28% ammonia and 4parts ammonium sulfocyani de B. A print paste is prepared as in A withthe exception that the 2-phenyl-benzotriazole-l-oxide is omitted andwater is substituted for'it.

Cotton prints are made from each of these printing compositions.

The cotton prints obtained from the composition A formulated-withZ-phenyl-benzotriazoled-oxide were tinctorially much stronger andbrighter than those obtained from B.

A print paste is prepared as follows: I

4 parts of a dry dyestufi composition-containing the disodium salt ofthe sulfuric acid ester of the dye of illustration 3 (equivalent to 1.04parts of'the parent vat dye) V V 1 part2-[4-hydroxyphenyllbenzotriazole-l-oxide 4 partsS,18'-dihydroxy-.diethyl sulfide 16 parts warm water and holding in aboiling Water bath for2 minutes v The solution is then mixed with 60parts starch tragacanth thickening and V 4 parts of a 35%sodium'chlorate solution I 2 parts 1% ammonium vanadate solution 2 parts28% ammonia 2 parts gluconic acid solution B. A print paste is preparedas in A with the exception that the 2-[4-hydroxyphenyllbenzotriazole-l-oxide is omitted.

B. A print paste is prepared as in A with the exception 7 that thel-acetyl benzotriazole is omitted. V .Cotton cloth is'printed with aportion of each of the printing pastes A and B. a The printing pasteprepared from the dyestufi composition A containing l-acetyl' benzotriazole yields prints that are stronger and brighter than thoseobtained from Printing composition B.

.Cotton cloth is printed with a portion of each of the printing pastes Aand B.

The printing paste A containing 2-[4-hydroxyphenyllbenzotriazole-l-oxide yields prints that arelstrongerand brighter than the prints obtained from printing composition B. 7 I pExample VIII A. A print paste is prepared as follows: 4 parts of a drypowder containing- 7 1.04 parts of the same parent vat dye used inExample VH 2 parts benzotriazole 4 parts B,fi-dihydroxy-diethy1 sulfideand 4 parts urea and finally dissolved by v I 15 parts warm water andholding in a water bath for 2 minutes 1 I f i A The solution is thenmixedwith a 60 parts starch tragacanth thickening and 1 4 parts 25%sodium chlorate solution l.

2 parts 1% ammonium vanadate solution 4 1 1 part 25 ammonia and 4.partsammonium sulfocyanide.

V B. A print paste isp repa'red as in Awith the exception Example IX A.A print paste is prepared from the following dyestufi composition.

4 parts of a dry dyestulf composition containing the disodium salt or"the sulfuric acid ester of the leuco compound of dibromo-dibenz-pyrene(equivalent to 1.0 part of the parent vat dye) The solution is thenmixed with:

60 parts of starch-tragacanth thickening and 4 parts of a 35% sodiumchlorate solution 2 parts 1% ammonium vanadate solution 2 parts 28%ammonia 2 parts 50% gluconic acid solution B. A print paste is preparedas in A with the exception that the benzotriazole is omitted and 18parts of water are used instead of the 16 parts used in A.

Cotton cloth is printed with a portion of each of the printing pastes Aand B.

The cotton prints obtained from the composition A formulated withbenzotriazole is stronger, smoother and brighter than those obtainedfrom B.

Another portion each of the printing pastes is permitted to stand for 7days, then printed. The prints made from the composition containingbenzotriazole were much stronger and smoother than those obtained fromthe composition Without benzotriazole.

Example X A. A print paste is prepared from the following dyestuficomposition.

10 15 parts of Warm Water and holding in a water bath for two minutesThe solution is then mixed with:

60 parts starch-tragacanth thickening and 4 parts 25% sodium chloratesolution 2 parts 1% ammonium vanadate solution 1 part 28% ammonia and 4parts ammonium sulfocyanate B. A print paste is prepared as in A withthe exception that the benzo'triazole is omitted and Water substitutedfor it.

Cotton prints are made from each of the printing compositions. w

The cotton prints obtained from the composition A formulated withbenzotriazole are stronger, brighter and smoother than those obtainedfrom B.

Another portion each of the printing paste is permitted to stand for 7days, then printed. The prints made from the composition containingbenzotriazole were stronger and brighter than those obtained from thecomposition without benzotriazole.

I claim:

1. A dyestuff composition comprising a salt of an acid polybasic acidester of a leuco vat dyestuflf and a benzo-' triazole selected from theclass consisting of the following formulae:

N n (Y N-R' and 3. A dyestuff composition according to claim 1 whereinthe benzotriazole is l-methyl benzotriazole.

4. A dyestuff composition according to claim 1 wherein the benzotriazoleis l-ethyl benzotriazole.

5. A dyestuff composition according to claim 1 wherein the benzotriazoleis l-hydroxy benzotriazole.

6. A dyestufi composition according to claim 1 wherein the benzotriazoleis 2-phenyl benzotriazole-l-oxide.

References Cited in the file of this patent UNITED STATES PATENTS2,024,502 Berthold Dec. 17, 1935 2,372,370 Duport Mar. 27, 19452,389,245 Wiazmitinow Nov. 20, 1945 2,406,586 Clark Aug. 27, 19462,540,799 Taras Feb. 6, 1951 2,559,807 To'pham July 10, 1951 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 2,940,815 June14., 1960 John Taras It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionand that the said Letters Patent should read as corrected below.

Column 4, line 50, formula (5)., .for that portion reading "-Cl read Clcolumn 5, line 73 Example I for "4 parts of a 35% sodium chloratesolution" read 4 parts of urea and Signed and sealed this 31st day ofJanuary 1961,

(SEAL) Attest:

KAR H AXLINE ROBERT C. WATSON Attesting Oificer Commissioner of Patents

1. A DYESTUFF COMPOSITION COMPRISING A SALT OF AN ACID POLYBASIC ACIDESTER OF A LUEOC VAT DYESTUFF AND A BENZOTRIAZOLE SELECTED FROM THECLASS CONSISTING OF THE FOLLOWING FORMULAE: